Direkt zum Inhalt

Yakubenko, Artyom A. ; Tupikina, Elena Yu. ; Antonov, Alexander S.

The Role of Conjugation in the Halogen−Lithium Exchange Selectivity: Lithiation of 4,6,7,9‐Tetrabromo‐1,3‐dimethyl‐2,3‐dihydro‐1H‐perimidine

Yakubenko, Artyom A. , Tupikina, Elena Yu. and Antonov, Alexander S. (2023) The Role of Conjugation in the Halogen−Lithium Exchange Selectivity: Lithiation of 4,6,7,9‐Tetrabromo‐1,3‐dimethyl‐2,3‐dihydro‐1H‐perimidine. Chemistry – A European Journal.

Date of publication of this fulltext: 26 Jul 2023 04:55
Article
DOI to cite this document: 10.5283/epub.54521


Abstract

The first case of successful suppression of the coordination of a lithium atom with a dialkylamino group by the effective conjugation of the latter with the aromatic core has been discovered. This effect controls regioselectivity of the bromine-lithium exchange in 4,6,7,9-tetrabromo-1,3-dimethyl-2,3-dihydro-1H-perimidine, which leads to products with the most effective conjugation. As a result, ...

The first case of successful suppression of the coordination of a lithium atom with a dialkylamino group by the effective conjugation of the latter with the aromatic core has been discovered. This effect controls regioselectivity of the bromine-lithium exchange in 4,6,7,9-tetrabromo-1,3-dimethyl-2,3-dihydro-1H-perimidine, which leads to products with the most effective conjugation. As a result, the product of this quadruple exchange demonstrates no tendency of the coordination of the NMe groups to neighboring lithium atoms despite the absence of steric restrictions. Experimental results are explained by means of quantum chemical calculations: geometry optimization, natural bond analysis and scans using the modredundant scheme.



Involved Institutions


Details

Item typeArticle
Journal or Publication TitleChemistry – A European Journal
Publisher:WILEY-V C H VERLAG GMBH
Place of Publication:WEINHEIM
Date1 June 2023
InstitutionsChemistry and Pharmacy > Institut für Organische Chemie
Identification Number
ValueType
10.1002/chem.202301439DOI
Keywords; organolithiums; conjugation; coordination; regioselectivity; naphthalene
Dewey Decimal Classification500 Science > 540 Chemistry & allied sciences
StatusPublished
RefereedYes, this version has been refereed
Created at the University of RegensburgPartially
URN of the UB Regensburgurn:nbn:de:bvb:355-epub-545215
Item ID54521

Export bibliographical data

Owner only: item control page

nach oben